Matrix-Assisted Laser Desorption/Ionization Mass Spectrometric Analysis of Uncomplexed Highly Sulfated Oligosaccharides Using Ionic Liquid Matrices

Abstract

Direct UV matrix-assisted laser desorption/ionization (MALDI) mass spectrometric analysis of uncomplexed, underivatized, highly sulfated oligosaccharides has been carried out using ionic liquids as matrices. Under conventionally used MALDI time-of-flight experimental conditions, uncomplexed polysulfated oligosaccharides do not produce any signal. We report that 1-methylimidazolium alpha-cyano-4-hydroxycinnamate and butylammonium 2,5-dihydroxybenzoate ionic liquid matrices allow the detection of picomole amounts of the sodium salts of a disaccharide, sucrose octasulfate, and an octasulfated pentasaccharide, Arixtra. The experimental results indicate that both analytes undergo some degree of thermal fragmentation with a mass loss corresponding to cleavage of O-SO3Na bonds in the matrix upon laser irradiation, reflecting lability of sulfo groups.

Tandem Mass Spectrometry of Tagged and Permethylated Polysaccharides

“…An example of spectroscopic application is the determination of pullulans. The combination of 2,5-DHB with butylamine (DHBB) turned out to be well suited for the analysis of oligosaccharides and glycolipids (Mank et al, 2004;Laremore et al, 2006Laremore et al, , 2007. The same ILM was used for www.intechopen.com…”

Liquid Matrices in MALDI-MS

“…A. & Armstrong, D. W., 2009;Fukuyama, Y. et al, 2008a;Kaneshiro, K. et al, 2011;Laremore, T. N. et al, 2006Laremore, T. N. et al, , 2007Mank, M. et al, 2004). Our group reported high sensitivity analyses of oligosaccharides using an optimized 1,1,3,3-tetramethylguanidine (TMG) salt of p-coumaric acid (G 3 CA) and a TMG salt of CHCA (G 2 CHCA) as liquid matrices (Fig.…”

Analysis of carbohydrates and glycoconjugates by matrix‐assisted laser desorption/ionization mass spectrometry: An update for the period 2005–2006

“…Although polysulfated sugars usually do not give signals under conventional MALDI conditions, the liquid matrices 1-methylimidazolium (4 þ 1/23) a-cyano-4-hydroxycinnamate and tetrabutylammonium (Bu 4 N þ 1/26) 2,5-dihydroxybenzoic acid have produced signals from sucrose octasulfate (5) and an octasulfated pentasaccharide as their sodium salts. No ion pairing was necessary but some loss of sulfate was seen (Laremore et al, 2006).…”